Chapter 4

The Chemistry of Hydrogen

Write the
• Electron configuration
• Period
• Group
• Block of hydrogen atom?
• It is difficult to give a proper place to hydrogen in
the periodic table. why?
because of its resemblance with halogens as well
as alkali metals.
• The dual behavior of hydrogen is attributed to its
electronic configuration.
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 Occurrence
• Hydrogen(H2) is the most abundant element in the
universe (70% of the universe’s total mass) .
• The giant planets Jupiter and Saturn consists mostly of
hydrogen.
• About half the mass of the sun and some other stars is
made up of hydrogen.
• It is the third most abundant element on the surface of
the globe. In the combined form it constitutes 15.4% of
the earth’s crust and the oceans.
• Earth does not possess enough gravitational pull to retain
light H2 molecules , so it is not in our atmosphere. In the
crustal rocks it is 10th in the order of abundance ~ 0.15%
by weight.

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Isotopes of hydrogen
• The three isotopes of hydrogen are protium ( 11H
), deuterium ( 21H or D) and tritium ( 31H or T ).
• The predominant form is protium whose atoms
are made up of a single proton and a single
electron.
• The deuterium nucleus is made up of a proton
and a neutron, giving it a mass number of 2.
• The tritium ( 31H ) concentration is about 1 atom
per 1018 atoms of protium.
• It is radioactive and emits low energy β-particles
(t½ 12.33 y).

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 Isomers of hydrogen
• Dihydrogen has two nuclear spin isomers called ortho and
para–dihydrogen.
• Their nuclei possess parallel and antiparallel spins
respectively.
• The two isomers have 1 and 0 nuclear spin respectively.
Conversion of one isomer into the other is a slow process.
• Para- hydrogen with lower energy is favored at low
temperatures.
• Above 0 K , the equilibrium concentration of the ortho isomer
increases until a limiting 3 : 1 proportion of ortho : para is
established.

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 Cont…
• It is possible to obtain pure para-hydrogen.
• It is never possible to obtain a sample containing
more than 75% ortho hydrogen.
• The physical properties of dihydrogen are not
significantly affected by nuclear spin isomerism.
Some of the notable difference are :
• The thermal conductivity of para-hydrogen is 50%
greater than that of the ortho-hydrogen.
• The melting point of para hydrogen is 0.15 K
below that of hydrogen contain 75% ortho-
hydrogen.

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 Resemblance and difference of hydrogen with
 Similarities alkali metals
 Both have one electron in valence shell.
 Both are electropositive and form positive ions i.e. H+ and Na+ etc.
 Both are hydrated in aqueous solution as H+, Li+ and Na+ etc.
 Both reacts with non metals to form similar type of compounds as H2O,
Na2O and HCl, NaCl etc

 Dissimilarities
 Hydrogen is gas whereas IA element are metal.
 H+ is unstable whereas Na+, Li+ are stable.
 Alkali metals don't form negative ions but Hydrogen i.e. H-
 Hydrogen forms covalent and ionic compounds whereas alkali metals only
form ionic compounds.
 Hydrogen exists as diatomic molecule (H2) where alkali don't.
 Hydrogen from neutral oxide (H2O) whereas alkali metals form basic
oxides (Na2O).

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 Resemblance and difference with halogens
 Similarities
Both are gases i.e. H2, F2, Cl2.
Both require one electron to complete their shell.
Both forms negative ions as H-, Cl-, Br-.
Metallic hydrides (NaH) as well as metallic halides (NaCl) are ionic.
Both exists as diatomic molecules i.e. H2, F2, Cl2.
Both forms covalent compounds with non-metals i.e. CH4, SiH4, CCl4.

 Dissimilarities
Hydrogen is colourless whereas halogens are coloured gases.
Hydrogen has one electron in valence shell (1s(1)), whereas halogens
have seven electrons (ns2np2).
Halogens don't form positive ions whereas hydrogen forms positive ions
H+.
H- is unstable whereas F-, Cl- are stable.
Hydrogen is reducing agent where halogens are oxidizing agents.
Hydrogen forms neutral oxides whereas halogens form acidic oxides.

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 Chemical properties of Hydrogen
•Hydrogen(H2) combines with halogens (X) to
give hydrogen halides.
•The reactivity of halogens towards dihydrogen
decreases in the order: F2> Cl2> Br2> I2.
• The reaction with fluorine takes place even in
dark ; with iodine a catalyst is required

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Reaction with oxygen
• Dihydrogen combines with dioxygen either at 970 K or
upon passing electric discharge to form water vapours.
• The reaction is highly exothermic.

Reaction with nitrogen

• Dihydrogen and dinitrogen combine to form ammonia
under following conditions.
• The method is used to manufacture ammonia by
Haber process.

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Action with metals
• Dihydrogen combines directly with alkali metals,
alkaline earth metals and certain rare earth metals to
form corresponding compounds known as hydrides.
• In these hydrides hydrogen exists in −1 state.
• Due to their ionic nature, these hydrides are also
referred to as salt like hydrides.
• The metals like iron , nickel, chromium, palladium etc.
absorb dihydrogen in almost stoichiometric quantities.
• This phenomenon is known as occlusion and the
compounds thus formed are known as interstitial
hydrides or metallic hydrides.

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 Cont…
• This phenomenon is known as occlusion and the
compounds thus formed are known as interstitial
hydrides or metallic hydrides.

• During the formation of these compounds

hydrogen atoms occupy the interstitial sites present
in the crystals of metals.

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 Reaction with metal ions
• Dihydrogen reduces some metal ions in aqueous
solutions into corresponding metals. For example,
Pd2+(aq) + H2(g) → Pd(s) + 2 H+(aq)
Reaction with metal oxides (reducing property)
• When dihydrogen gas is passed over heated metal
oxides it reduces them into corresponding metals.
• Thus it acts as a strong reducing agent. Some examples
showing the reducing action of dihydrogen are as follows.

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 Reaction with carbon monoxide
• Dihydrogen reacts with carbon monoxide at 700 K and 200
atmosphere pressure in presence of ZnO / Cr2O3 catalyst to
form methanol.

Reaction with metal oxides (reducing property)

• When dihydrogen gas is passed over heated metal oxides it
reduces them into corresponding metals.
• Thus it acts as a strong reducing agent. Some examples
showing the reducing action of dihydrogen are as follows.

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Hydrides
• Dihydrogen , under certain reaction conditions ,
combines with almost all elements , except noble
gas to form binary compounds, called hydrides.
• If ‘ E ’ is the symbol of an element then hydride
can be expressed as EHx ( e.g., MgH2 ) or EmHn
( e.g., B2H6)
The hydrides are classified into three categories :
• Ionic or saline or salt like hydrides.
• Covalent or molecular hydrides
• Metallic or non-stoichiometric hydrides

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 Saline hydrides (Ionic hydrides)
• These are compounds of hydrogen with most of the s-
block elements.
• They are non-volatile, non-conducting , crystalline solids.
• They are also referred to as ‘salt like’ hydrides. However,
BeH2 and MgH2have covalent polymeric structures.
• The binary hydrides of alkali metals (LiH, NaH, KH , RbH,
CsH ) have rock salt structures.
• The thermal stability of alkali metal hydrides decreases
from LiH to CsH.
• The order of stability in the alkaline earth metal hydrides
is :
CaH2 > SrH2> BaH2

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 Molecular hydrides( Covalent hydrides)
• Dihydrogen forms molecular compounds with most of p-
block elements.
• Most of the familiar examples are CH4 , NH3 , H2O and HF.
• For convenience hydrogen compounds of non-metals have
also been considered as hydrides.
• Being covalent, they are volatile compounds.
• The systematic name for molecular hydrides are usually
formed from the name of the element and the suffix –ane .
• Phosphane for PH3 , oxidane for H2O and azane for NH3.

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 Metallic Hydride or Non-stiochiometric
(Interstitial ) Hydrides
• These hydrides are formed by d-block (Groups 3, 4 and 5)
and f-block elements.
• In Group 6 chromium alone forms the hydride CrH.
• The metals of group 7, 8 and 9 do not form hydrides.
• The region of the periodic table from group 7 to 9 is
referred to as the Hydride Gap.
• These hydrides conduct heat and electricity though not
as efficiently as their parent metals do.
• Unlike saline hydrides, they are almost always non-
stoichiometric , being deficient in hydrogen.

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 Cont…
• For example, LaH2.87 , YbH2.55 , TiH1.5 –1.8 , ZrH1.3 –
1.75, VH0.56 , NiH0.6–0.7 , PdH0.6–0.8 etc.
• In such hydrides , law of constant composition
does not hold good.
• Earlier it was thought that in these hydrides ,
hydrogen occupies interstices in metal lattice
producing distortion without any change its type.
• Consequently, they were termed as interstitial
hydrides.

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 Preparation of hydrogen
• Small scale Production of Dihydrogen
• In the laboratory , dihydrogen can be prepared very
conveniently by the action of dilute sulphuric acid on
granulated zinc even at room temperature.
Zn(s) + H2SO4 (dil) → ZnSO4 + H2 (g)
The apparatus used for this purpose is shown in Fig.

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 Industrial production of dihydrogen
• By the Electrolysis of Acidified water Hydrogen is
manufactured by the electrolysis of acidified water
using platinum electrodes.
• Hydrogen of high purity (> 99.95% ) is obtained by
electrolysing warm aqueous barium hydroxide
between nickel electrodes.
• From hydrocarbons and coke Hydrogen is obtained
by the reaction of steam on hydrocarbons or coke at
high temperatures.
• The mixture of CO and H2 is used in the synthesis of
methanol and a number of hydrocarbons, it is also
called synthesis gas or ‘syngas’.
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 Cont…
• Hydrogen can also produced as a by-product of the
brine electrolysis for the manufacture of chlorine and
sodium hydroxide.
• During electrolysis , the reactions that take place
at anode : 2Cl− (aq) → Cl2 + 2 e−
at cathode : 2H2O(l) + 2 e− → H2(g) + 2OH− (aq)
The overall reaction is :
2Na+(aq) + 2Cl− (aq) + 2 H2O(l) → Cl2(g) + H2(g) + 2
Na+(aq) + 2OH− (aq)

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 Use of hydrogen

• The most important use of dihydrogen is in the

manufacture of ammonia by Haber process.
• Dihydrogen is used in the manufacture of methanol.
• Direct reaction of dihydrogen with chlorine is used for
the preparation of hydrogen chloride.
• Dihydrogen is used in the manufacture of metal
hydrides.
• In metallurgical processes, it is used to reduce heavy
metal oxides to metals.

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 Cont…
• An important use of hydrogen is in the atomic hydrogen and
oxy-hydrogen torches for cutting and welding.
• Dihydrogen is dissociated with the help of an electric arc and
the hydrogen atoms obtained are allowed to recombine on
the surface to be welded.
• High temperature of 4000 K is generated.
• Hydrogen is used as a fuel in space rockets and guided
missiles.
• Hydrogen is used in H2− O2 fuel cells

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 UNIQE PROPRTIES OF WATER
• Each oxygen can form two hydrogen bonds with the
hydrogen atoms of the neighbouring molecules.
• Thus in liquid state, water consists of aggregates of
varying number of H2O molecules held together by
hydrogen bonds.
• The presence of aggregates of molecules due to
hydrogen bonding affects several properties of water to a
considerable extent.
• The existence of water in liquid state ,

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 Cont…
• its exceptionally high boiling point as compared to
other hydrides of the elements of Group 6 and many
more curious properties of water may be attributed
to the presence of hydrogen bonding in it.
• In solid state , the water molecules come still closer
and get arranged tetrahedrally.
• The solid form of water, i.e., exists in different
crystalline forms depending upon the conditions
used for freezing water

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 Cont…
• The structure of normal hexagonal is shown in
Fig. In this type of ice, each oxygen atom is
tetrahedrally surrounded by four other oxygen
atoms through a hydrogen atom.

Fig.Structure of normal hexagonal ice 26

 Water shows a varied and unique chemical behaviour.
• Amphoteric behaviour :
• It has the ability to act as an acid or a base, in Bronsted
sense, that is, it behaves as an amphoteric substance.
• It can for example, act as an acid towards ammonia :
H2O(l) + NH3 (aq) → OH−(aq) + NH4+(aq)
And as a base towards H2S :
H2S(aq) + H2O(l) → H3O+(aq) + HS−(aq)
• In general, water can act as a base towards acids stronger
than itself and as an acid towards a base stronger than it.
• The auto-protolysis of water represented by :
H2O(l) + H2O(l) → H2O+(aq) + OH−(aq)
Acid 1 base 2 acid 2 base 1
• is of great importance in acid-base chemistry.

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 Cont…
• Each hydrogen is covalently bonded to one oxygen
atom and linked to another oxygen atom by a
hydrogen bond.
• This type of packing leads to an open cage structure
with large open spaces.
• This is why the density of ice is less than that of
water and it floats on water

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